Synthesis, catalytic activity, and photophysical properties of 5,6-membered Pd and Pt SCS′-pincer complexes based on thiophosphorylated 3-amino(hydroxy)benzoic acid thioanilidesElectronic supplementary information (ESI) available: Fragment of packing in the molecule 3, the absorption spectra of ligands 3, 7 and their Pd and Pt pincer complexes 8a,b, 9a,b, and the excitation and emission spectra of complex 9b at 77 K, the luminescence spectra of ligands 3,7, and complex 9a at 77 K, and the result

• Main Authors: Aleksanyan, D. V, Kozlov, V. A, Nelyubina, Y. V, Lyssenko, K. A, Puntus, L. N, Gutsul, E. I, Shepel, N. E, Vasil'ev, A. A, Petrovskii, P. V, Odinets, I. L
• Format: Journal Article
• Language: English
• Published: 01.02.2011
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c0dt01154a

Novel unsymmetrical SCS ′-pincer ligands, 1-[PhNHC(S)]-3-[Ph 2 P(S)NH]-C 6 H 4 ( 3 ) and 1-[PhNHC(S)]-3-[Ph 2 P(S)O]C 6 H 4 ( 7 ), bearing a thiocarbamoyl moiety in combination with thiophosphorylamino- and thiophosphoryloxy-donating groups, respectively, were obtained via thiophosphorylation of 3-amino- and 3-hydroxy-benzoic acid (thio)anilides 1 and 6 . Direct cyclometallation of the central benzene ring in the ligands 3 and 7 in reaction with (PhCN) 2 MCl 2 (M = Pd, Pt) as a metal precursor afforded κ 3 - SCS ′-hybrid pincer complexes 8 , 9 with 5- and 6-membered fused metallacycles in good to high yields (67-95%). The complexes 8 and 9 were characterized by multinuclear NMR ( 31 P, 1 H, 13 C) and IR spectroscopy as well as single-crystal X-ray crystallography. Palladium complexes 8a and 9a were shown to be active catalysts for the Suzuki-Miyaura cross-coupling reaction. In the solid state the ligands 3 and 7 as well as their Pt( ii ) and Pd( ii ) complexes 8 and 9 are luminescent at 300 K. The emission of the complexes has the different origin depending on the metal nature. Novel hybrid Pd and Pt SCS′-pincer complexes with fused 5,6-membered metallacycles were obtained and structurally characterized. Pd-complexes are highly active catalysts for the Suzuki reaction and both Pd and Pt complexes exhibit luminescent properties at 300 K.